WO2013123678A1 - Conversion de lipides - Google Patents

Conversion de lipides Download PDF

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Publication number
WO2013123678A1
WO2013123678A1 PCT/CN2012/071759 CN2012071759W WO2013123678A1 WO 2013123678 A1 WO2013123678 A1 WO 2013123678A1 CN 2012071759 W CN2012071759 W CN 2012071759W WO 2013123678 A1 WO2013123678 A1 WO 2013123678A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
process according
reactor
lipid
sapo
Prior art date
Application number
PCT/CN2012/071759
Other languages
English (en)
Inventor
Zhijian Tian
Congxin WANG
Lei Wang
Bingchun Wang
Lijun Yan
Wei Qu
Peng Li
Huaijun Ma
Renshun XU
Original Assignee
Dalian Institute Of Chemical Physics Chinese Academy Of Sciences
Bp P.L.C.
Petrochemical Research Institute, Petrochina
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute Of Chemical Physics Chinese Academy Of Sciences, Bp P.L.C., Petrochemical Research Institute, Petrochina filed Critical Dalian Institute Of Chemical Physics Chinese Academy Of Sciences
Priority to AU2012371109A priority Critical patent/AU2012371109B9/en
Priority to US14/379,187 priority patent/US20150203417A1/en
Priority to EP12869155.7A priority patent/EP2817275B1/fr
Publication of WO2013123678A1 publication Critical patent/WO2013123678A1/fr

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    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
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    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/83—Aluminophosphates (APO compounds)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to the conversion of organic materials, in particular to the conversion of lipids. Aspects of the invention relate to the production of a hydrocarbon product.
  • a conversion process converts a lipid feedstock to form a hydrocarbon product.
  • the hydrocarbon product includes alkanes.
  • the product formed has high proportion of branched alkanes.
  • the product formed has a controlled proportion of branching.
  • the product is suitable for use as, or as a component in middle distillate, including for example diesel fuels and/or jet fuels.
  • the lipids are obtained from a biological source.
  • aspects of present invention disclose a process for producing biodiesel and/or bio-jet from lipids, where main components of the biodiesel comprise iso-paraffins.
  • Preferred aspects of the invention relate to the catalytic conversion of organic materials, for example lipids, preferably to form a product suitable for use in the
  • Biodiesel produced from a renewable resource such as vegetable oil and/or animal fat is another alternative energy source receiving interest.
  • first generation of biodiesel fuels examples of such fuels were based on fatty acid methyl ester (FAME) which was obtained from lipid and methanol via transesterification.
  • FAME fatty acid methyl ester
  • Such fuels have been commercialized.
  • the feedstock for the production of FAME must normally contain a low content of free fatty acid and water, and the acid or base component generated in the manufacture process is harmful to environment.
  • the main components of the first generation biodiesel are unsaturated esters with relatively low stability, low energy value, high viscosity and high freezing point.
  • the first generation biodiesel when used as an engine fuel, it must normally be blended with diesel derived from fossil fuel, often less than 20%, or even less than 10% of the fuel volume.
  • diesel derived from fossil fuel often less than 20%, or even less than 10% of the fuel volume.
  • the biodiesel comprises diesel-range
  • hydrocarbons derived from a lipid feedstock via hydrogenation and deoxygenation The lipid feedstock comprises for example triglyceride, glyceride and/or fatty acid (and possibly other components).
  • the renewable lipid feedstock typically have fatty acid carbon chains of 12-24 carbon atoms, mainly of 16-18 carbon atoms.
  • the product obtained is generally a mixture of hydrocarbons having the main components of Cn-C 24 paraffins.
  • the second generation biodiesel there are many potential advantages of the second generation biodiesel as compared with the first generation biodiesel. Firstly, existing refineries can directly be utilized for producing the second generation biodiesel. Also, the composition of the second generation biodiesel is similar to that of the fossil fuel diesel, and the viscosity and energy value are close to those of the fossil diesel, moreover, the cetane value is much higher (greater than 70) and the sulfur content is much lower (below 10 ppm) compared with first generation biodiesel. Furthermore, since the main components of the second generation biodiesel are saturated hydrocarbons, the storage and transportation of the second generation biodiesel are very stable compared with for first generation biodiesel. In addition, in some cases, an early boiling fraction of the second generation biodiesel may be used in biojet fuel. In some examples, the biodiesel is substantially fungible so can be blended with existing refinery diesel and can use the same storage and distribution networks.
  • a desirable product of the hydrotreatment process for producing diesel-range fuel from lipid is Cn-C 24 iso-paraffin (branched alkane) with high cetane value and low freezing point.
  • the catalyst used in the conventional hydrotreatment process for producing diesel-range paraffins from lipid is a NiMo or CoMo sulfide catalyst over which high amount of water is generated.
  • the hydro-treating catalysts described make n-paraffins and iso-paraffins. Subsequently, to obtain improved cold flow properties, an isomerization catalyst or component is used.
  • European Patent No. 1396531 International Patent Application No. WO2009156452
  • International Patent Application No. WO2008058664 International Patent Application No.
  • the general reaction process is as follows: the first step is a combined
  • the second step is a hydroisomerization step in which purified normal-paraffins are hydroisomerized for producing iso-paraffins.
  • the lipid is saturated and deoxygenated to produce normal alkanes, water, propane, carbon monoxide, carbon dioxide and other byproducts in the
  • the two-step process generally produces product having a high cetane value and low freezing point, and the low temperature performance of the product is good when it is used as diesel.
  • the two-step process consists of multiple units in which the hydrogenation, deoxygenation or hydroisomenzation proceeds individually over different catalysts.
  • the two-step process generally consumes a large amount of hydrogen and needs a relatively large investment for the manufacture of system equipment.
  • the lipids could be converted to form paraffins, for example iso-paraffins, in a single-step process.
  • the lipid would need to be converted to iso- paraffins through hydrogenation, deoxygenation and hydroisomerization simultaneously over a single catalyst in a single step.
  • pathway I The carboxyl group of the triglyceride is removed by releasing carbon monoxide and water, and normal-paraffin with one carbon less than the fatty acid group is produced via hydrodecarbonylation as illustrated in pathway II. Also, the carboxyl group of the triglyceride is removed by releasing carbon dioxide, and normal-paraffin with one carbon less than the fatty acid group is produced via hydrodecarboxylation as illustrated in pathway III. In these three pathways, 6 molar quantities, 3 molar quantities and 0 molar quantities of water are produced, respectively.
  • the lipid conversion to paraffins proceeds through different pathways over different metal/y-Al 2 03 catalysts.
  • the hydrodecarboxylation reaction is seen to be preferred over the ⁇ / ⁇ - ⁇ 1 2 ⁇ 3 catalyst, while the hydrodeoxygenation is preferred over the ⁇ / ⁇ - ⁇ 1 2 0 3 catalyst.
  • the activity of the catalyst can also be improved when the loading amount of the active metal component increased as reported in Ind. Eng. Chem. Res. 45 (2006) 5708-5715 and Green Chem. 12 (2010) 463-467.
  • the term lipid preferably includes, but preferably not exclusively includes, fatty acids, fatty acid derivatives, triglycerides, diglycerides, monoglycerides and phospholipids, fatty acid esters and/or a mixture of two or more of such compounds.
  • the lipid compound or compounds are obtained from a biological source, either directly or indirectly.
  • the lipid may for example include a plant derived fatty acid, for example a plant-derived fatty acid containing carbon chain unsaturation.
  • the lipid may or may not be pure.
  • the lipid may include sugars and/or other components.
  • aspects of the present invention find application in relation to the production of a hydrocarbon product from a feedstock containing a lipid, for example one or more fatty acid esters.
  • the feedstock may include one or more other components.
  • a process for producing a hydrocarbon product comprising contacting a feedstock with a catalyst composition in the presence of hydrogen, the feedstock including a lipid, and the catalyst composition being active for conversion of the lipid to the hydrocarbon product in a single step, the catalyst composition comprising an Ml -[Sup] catalyst, where Ml is an active metal and [Sup] comprises an acidic support, wherein the hydrocarbon product includes greater than 70 % measured by weight of Cn-C 24 alkanes based on the weight of the lipid, and the content of branched alkanes of the Cn-C 24 alkanes is greater than 60 % measured by weight of branched Cn-C 24 alkanes based on the weight of the Cn-C 24 alkanes.
  • Examples of the present invention provide a process in which, catalytically hydrogenating, deoxygenating and hydroisomerizing a lipid feedstock to paraffins may be carried out in a single step.
  • oxygen atoms of the lipid in examples of the invention are mainly converted to CO and C0 2 , and less are converted to H 2 0.
  • the single-step process of examples of the invention described herein may produce biodiesel with high cetane value, low freezing point, low aromatics and low sulfur.
  • the hydrogen consumption of the process may be less than that of the conventional two-step hydrogenation process.
  • the oxygen atoms of lipid will mainly be removed by releasing carbon monoxide and water through hydrodecarbonylation and by releasing carbon dioxide through hydrodecarboxylation. Therefore, the process of examples of the invention produces less water than conventional processes. Water is potentially harmful to isomerizing active sites of the catalyst, and thus in examples of the present invention, the generated paraffins may be isomerized simultaneously over the same catalyst.
  • the hydrogen consumption of the present single-step process is less than that of the two-step hydrogenation process.
  • catalytically hydrogenating, deoxygenating and hydroisomerizing of the lipid feedstock to alkanes are carried out in a single step, for example over a single catalyst composition, for example in a fixed-bed reactor.
  • the maximum theoretical paraffins yield is determined to be 86.8wt.% assuming the trilinolein is converted to octadecane via hydrodeoxygenation, or 82.0wt.% assuming the trilinolein is converted to heptadecane via hydrodecarbolylation or hydrodecarboxylation pathway.
  • the maximum theoretical paraffins yield is 84.1wt.% assuming the tripalmitylglycerol is converted to hexadecane via hydrodeoxygenation, or 78.9wt.% assuming the
  • tripalmitylglycerol is converted to pentadecane via hydrodecarbonylation or
  • catalytic hydrogenation, deoxygenation and hydroisomerization are carried out substantially simultaneously in the same reactor.
  • there is no separation step within the reactor for example to separate target products (for example iso-paraffins), intermediate products (for example normal-paraffins, organic oxygenates) and byproducts (for example CO, C0 2 , C 3 H 8 , H 2 0) in the process of the reaction.
  • target products for example iso-paraffins
  • intermediate products for example normal-paraffins, organic oxygenates
  • byproducts for example CO, C0 2 , C 3 H 8 , H 2 0
  • the oxygen atoms of lipid feedstock are mainly converted to CO and C0 2 through hydrodecarbonylation and hydrodecarboxylation, and less are converted to H 2 0 through hydrodeoxygenation.
  • the poison effect induced by the water to the hydroisomerisation catalyst component may be reduced which can allow for the hydrogenation, deoxygenation and hydroisomerization of the feedstock to be combined into a single step.
  • the substrate is a Bransted acid.
  • Examples of the invention described herein include description of methods for preparation of catalyst compositions. Some aspects of the invention extend to the case in which the catalyst composition is prepared using other methods or from different sources.
  • the catalyst is a multifunctional catalyst.
  • the catalyst is active for catalytically hydrogenating, deoxygenating and hydroisomerizing the lipid feedstock.
  • the catalyst is active to effect hydrogenation, deoxygenation and
  • the majority of the oxygen atoms of the lipid feedstock are converted to CO and C0 2 through hydrodecarbonylation and hydrodecarboxylation, the minority being converted to H 2 0 through hydrodeoxygenation.
  • the hydrodecarbonylation plus hydrodecarboxylation selectivity of the conversion reaction of the lipids is greater than 50%.
  • the selectivity of the conversion reaction is determined from an analysis. Without wishing to be bound by any particular theory, it is believed that the ratio of C 0 dd to C eV en in the products is an indication as to the selectivity of the conversion reaction to hydrodecarbonylation plus
  • hydrodecarboxylation It is understood that the hydrodeoxygenation conversion reaction would generally produce a different length carbon chain alkane compared with the hydrodecarbonylation and hydrodecarboxylation reactions. In examples, one of the former pathway and the latter pathways would produce odd and even carbon backbone alkanes.
  • a measure of the selectivity of the conversion reaction can be made.
  • a hydrodeoxygenation conversion reaction would generally produce C eV en alkanes, where the hydrodecarbonylation and
  • the weight ratio of C 0 dd alkanes to C even alkanes in the hydrocarbon product is greater than one, where C 0 dd alkanes comprise an odd number of carbons, and
  • Ceven comprise an even number of carbons.
  • the ratio of odd-numbered paraffins product to even-numbered paraffins product is greater than one.
  • the catalyst is a type of metal/acidic support solid bifunctional catalyst with high hydrogenation activity, high hydrodecarboxylation or hydrodecarbonylation activity, and high hydroisomerization activity.
  • the catalyst comprises a metal/acidic support solid catalyst.
  • the catalyst may comprise a bifunctional catalyst.
  • the acidic support comprises a zeolite and/or a substituted
  • aluminophosphate preferably a SAPO or a MeAPO.
  • the acidic substrate comprises an Ml-zeolite or an Ml -(substituted aluminophosphate AlPO-n), for example Ml-silicoalumino phosphate (SAPO) catalyst (where Ml is a metal component).
  • SAPO Ml-silicoalumino phosphate
  • the SAPO comprises a crystalline microporous silicoalumino phosphate composition.
  • Silicoalumino phosphates are known to form crystalline structures having micropores which compositions can be used as molecular sieves for example as adsorbents or catalysts in chemical reactions.
  • SAPO materials include microporous materials having micropores formed by ring structures, including 8, 10 or 12-membrered ring structures.
  • Some SAPO compositions which have the form of molecular sieves have a three- dimensional microporous crystal framework structure of P0 2 + , A10 2 " , and Si0 2 tetrahedral units.
  • the ring structures give rise to an average pore size of from about 0.3 nm to about 1.5 nm or more.
  • SAPO molecular sieves and methods for their preparation are described in US 4440871 and US6685905 (the relevant content of which is
  • the zeolite comprises a microporous aluminosilicate material.
  • the substituted aluminophosphates comprises a microporous crystalline material in which the Al and/or P is substituted for other elements, for example Si, Mg, Mn, Co, Zn, to form for example SAPO-n and/or MeAPO-n materials.
  • the acidic support comprises one or more selected from the group comprising SAPO-5, SAPO-11, SAPO-31, SAPO-34, SAPO-41, MeAPO-5, MeAPO-11, MeAPO-31, ZSM-5, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-48 or mixtures thereof, preferably SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48 or mixtures thereof.
  • the acid support comprises one or more of the group comprising SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48.
  • the acidic support may comprise a mixture of two or more zeolites and/or SAPOs.
  • the catalyst includes between from about 70 to 99.9 wt.% of [Sup] based on the weight of the catalyst.
  • the catalyst may include up to 99.8 wt.% of [Sup]. In some examples of the invention, the catalyst may include at least 70 wt.% of [Sup]. In some examples of the invention, the catalyst may include up to 30 wt.% of the metal.
  • the catalyst may include further components in addition to the metal Ml and acidic support [Sup].
  • aspects of the invention may be applicable to catalysts including other support materials, for example other microporous compositions, for example microporous compositions other than zeolites and SAPOs.
  • the catalyst may include metal organosilicates, silicalites and/or crystalline aluminophosphates.
  • the acidic support may include a molecular sieve, or a crystalline microporous material.
  • Ml is selected from one or more of the group comprising cobalt, molybdenum, nickel, tungsten, palladium, platinum, iridium, rhodium, rhenium, ruthenium, tin, copper, zinc.
  • Ml is selected from one or more of the group comprising platinum, palladium, molybdenum, tungsten, cobalt, nickel, tin and copper.
  • the catalyst composition comprises only one metal Ml on the support. In other examples, a mixture of more than one metal Ml may be used.
  • the weight percent of metal Ml present in the acidic support where Ml comprises platinum, palladium, tin or copper is between from about 0.1 to 10wt.%, preferably between from about 0.2 to 5 wt.% based on the weight of the catalyst.
  • the weight percent of metal Ml present in the acidic support where Ml comprises cobalt, nickel, molybdenum or tungsten is between from about 1 to 30 wt.%, preferably between from about 2 to 20 wt.% based on the weight of the catalyst.
  • the catalyst includes at least 0.2 wt.% of the metal. Preferably the catalyst includes not more than 30 wt.% of the metal.
  • the metal/acidic support solid catalyst is prepared using an impregnation method.
  • the acidic support [Sup] comprises a zeolite and/or SAPO and further comprises a refractory inorganic oxide.
  • the acidic support is formed by mixing a zeolite and/or SAPO with a refractory inorganic oxide.
  • the method of forming the acidic support includes the step of extruding and heating the mixture of zeolite/SAPO and refractory inorganic oxide.
  • the heating step may include a calcination treatment.
  • the heating treatment may for example proceed as follows: the extruded acidic support is preheated under oxygen or air atmosphere at between from about 100 to 150 ° C for 1 to 4 h, and then it is calcined under oxygen or air atmosphere at between from about 300 to about 600 ° C, for example between from about 500 to about 600 ° C for 4 to 12 h.
  • the resulting heat-treated mixture is preferably subsequently shaped.
  • a further aspect of the invention provides a process for producing a hydrocarbon product, the process comprising contacting a feedstock with a catalyst composition in the presence of hydrogen, the feedstock including a lipid, and the catalyst composition being active for conversion of the lipid to the hydrocarbon product in a single step, the catalyst composition comprising an Ml -[Sup] catalyst, where Ml is an active metal and [Sup] comprises an acidic support, wherein the acidic support includes a zeolite and/or SAPO, and a refractory inorganic oxide.
  • the zeolite/SAPO support has been treated to alter its acidity, its pores and/or channels.
  • a method or preparation of the acidic support includes carrying out an acid or alkali treatment.
  • the pore diameter of the zeolite or SAPO is smaller than the molecular diameter of the reactants.
  • the pore diameter of SAPO-11 and ZSM-22 is about 0.40 nm x 0.65 nm and 0.46 x 0.57 nm, respectively, while the dynamic molecular diameter of the triglyceride in examples of the invention is greater than 0.6 nm.
  • the reactants cannot generally access the inside of the micropores.
  • the deoxygenation reaction can only be carried out on the outer surface of the zeolite crystals.
  • the outer surface of the zeolite crystals is usually very small.
  • an effect of the addition of the refractory inorganic oxide is to enhance the outer surface of the catalyst by building some hierarchical pores through which the reactants can access more active sites of the catalyst.
  • the refractory inorganic oxide is selected from the group comprising alumina and silica, or mixtures thereof.
  • the refractory inorganic oxide is present in an amount of between from about 20 to 60wt.% based on the weight of the catalyst.
  • the product of the conversion is a biodiesel and/or component for use in a biodiesel and/or biojet.
  • the product may undergo further processing and/or blending, for example to form a biodiesel product and/or a biojet product.
  • the majority of the hydrocarbon product is preferably Cn-C 24 paraffins, especially isomers of paraffins.
  • a target product is biodiesel and/or biojet.
  • the product includes mainly paraffins with a number of carbon atoms ranging from 11 to 24, especially isomers.
  • the yield of Cn-C 24 paraffins is in some preferred examples of the invention greater than 70wt.% based on the weight of the lipid feedstock.
  • the isomers content of Cn-C 24 paraffins is greater than 60wt.%.
  • Liquid product from the reaction may for example be analyzed by GC and/or GC-MS.
  • Gas product from the reaction may be analyzed by GC.
  • the components of the hydrocarbon product are mainly C 15 -C 18 paraffins preferably with a yield of 60wt.% or more based on the lipid feedstock.
  • the isomers content of C 15 -C 18 paraffins is greater than 60wt.%.
  • hydrocarbon product preferably comprises no more than 5wt.% C 6 -Cio paraffins and no more than lwt.% cycloalkanes.
  • the lipid feedstock comprises a triglyceride, glyceride and/or fatty acid.
  • the lipid is selected from the group comprising vegetable oil, animal fat, and waste oil or mixtures thereof.
  • the vegetable oil may be selected for example from the group comprising rapeseed oil, peanut oil, soybean oil, corn oil, rice oil, rice bran oil, safflower oil, palm oil, jatropha oil, castor oil, coconut oil, tall oil and olive oil or mixtures thereof.
  • the animal fat may be selected for example from the group comprising lard oil, tallow oil, suet oil, chicken oil, fish oil and train oil or mixtures thereof.
  • the materials for use as feedstock are not limited to refined oils.
  • the feedstock may include waste oil and/or by-product of a processing operation, for example a vegetable oil processing operation producing a product having a high free fatty acid (FFA) content.
  • FFA free fatty acid
  • the lipid feedstock may be derived from any suitable source, preferably a biological source, for example a plant or animal source.
  • the lipid feedstock includes components selected from the group consisting of vegetable oil, animal fat, waste oil, or mixtures thereof.
  • the feedstock may include other components in addition to lipids.
  • the process will be operated at appropriate temperature and pressure.
  • the preferred temperature of the process will be between from about 250 °C to 450 °C, for example 280 °C to 450 °C, for example 250 °C to 400 °C. Variations in temperature may occur across the catalyst, and preferably the average temperature across the catalyst is within that range of temperatures.
  • the pressure of the process may be for example between from 100 to 10000 kPa, for example between from 1000 to 10000 kPa, for example between from 2000 to 8000 kPa.
  • the hydrogen/oil ratio may be in the range of from 300 to 3000 L/L, for example between from 700 to 2000 NL/L.
  • the LHSV will be for example from about 0.1 to 5.0 h "1 .
  • the process includes catalytically hydrogenating, deoxygenating and hydroisomerizing the lipid feedstock to paraffins in a single step, at a temperature of between from about 250 to 400 ° C, a pressure of between from about 1000 to 10000 kPa, a LHSV between from about 0.1 to 5.0 h _1 .and a hydrogen/oil ratio of between from about 300 to 3000 L/L.
  • the conversion process itself does not include a separation stage, for example for separating normal-paraffins, iso-paraffins from water and/or other byproducts in the conversion process.
  • a separation stage for example for separating normal-paraffins, iso-paraffins from water and/or other byproducts in the conversion process.
  • the majority of, and preferably substantially all of any separation of products from the process is carried out after the conversion of the lipid to the hydrocarbon product.
  • the produced paraffins may be subsequently subject to a separation process.
  • the paraffins product may be distilled into fractions, for example for biojet and biodiesel.
  • hydroisomerisation are carried out substantially simultaneously in the same reactor.
  • target products for example iso-paraffins
  • intermediate products for example normal-paraffins
  • organic oxygenates for example CO, C0 2 , C33 ⁇ 4, H 2 0 in the reaction process.
  • by-products for example CO, C0 2 , C33 ⁇ 4, H 2 0 in the reaction process.
  • the process includes the step, after the conversion of the lipid to the hydrocarbon product, of separating the products.
  • the products are separated in one or more than one product separator after the single-step reaction.
  • hydrogen may be recycled into the reactor, for example carbon dioxide may be separated from a recycle hydrogen stream.
  • a purge may be carried out of hydrogen, propane, methane and/or carbon monoxide may be carried out for example to control levels of non-hydrogen components.
  • the reactor comprises a fixed-bed reactor.
  • the reactor comprises a reactor system which may comprise one or more than one reactor element.
  • one or more than one type of catalyst can be loaded in the reactor or reactor element.
  • the reactor of the present process may comprise a plurality of fixed-bed reactors in examples of the invention.
  • the catalytic conversion may be carried out in a reactor system in which the reactor system comprises one or more reactor elements.
  • the reactor or a reactor element of the system may contain a further catalyst composition.
  • the further catalyst composition may comprise an M2-[Supi] catalyst, where M2 is an active metal and [Supi] comprises an acidic support. M2 may be the same as or different from Ml . [Supi] may be the same as or different from [Sup].
  • the reactor system may comprise two or more reactor elements, the two or more reactor elements containing different catalyst compositions.
  • one or more of the reactor beds may include more than one catalyst
  • the different beds may include the same or different catalysts, in any appropriate combination.
  • the conversion may be carried out in a single reactor or reactor element, or across two or more reactors or reactor elements.
  • the conversion may be carried out over a single catalyst composition, or may be carried out over a plurality of catalyst compositions.
  • all of the catalyst compositions over which the conversion takes place may have a composition of M-[Sup], where M is preferably as described herein in relation to Ml, and/or where [Sup] is preferably as described herein.
  • the compositions of the catalysts may be the same or different.
  • the single step conversion is a conversion in which substantially no conversion products are removed until after the conversion of the lipid to the hydrocarbon product.
  • a single step conversion preferably there is substantially no separation of products during the conversion of lipid feedstock to paraffins.
  • the single step conversion may or may not include the addition of compositions, streams or other material during the conversion.
  • a hydrogen- containing stream may be added to or upstream of a reactor, or to or upstream of a reactor element such that hydrogen is added during the single step conversion.
  • reaction conditions may be changed during the single step conversion, for example with regard to temperature, pressure, space velocity, or other condition.
  • there is substantially no change of one or more reaction conditions during the single step conversion for example substantially no change in one or more of temperature, pressure, space velocity, during the single step conversion.
  • the feedstock contacts with the metal/acidic support solid bifunctional catalyst under hydrogen, hydrogen/nitrogen or hydrogen/inert gas atmosphere.
  • reaction conditions comprise one or more of the following: a temperature of 200 to 400 " C, a pressure of 1000 to 10000 kPa, a LHSV of 0.1 to 3.0 h "1 and a
  • a hydrogen-rich stream is separated from the products and hydrogen is returned to the reactor.
  • the hydrogenation, deoxygenation and hydroisomerisation of the feedstock may be combined by a single step by increasing the selectivity of hydrodecarboxylation and hydrodecarbonylation.
  • a product having a cetane value greater than 70, a freezing point below 0 ° C and a sulfur content less than 10 ppm may be produced in some examples.
  • the hydrogen and energy consumption may be reduced in some single-step processes as compared with at least some of the existing two-step process.
  • the related process may provide in some cases a new strategy for producing fungible energy from renewable resources.
  • the capital cost for a plant using a single step process may be lower than the capital cost for a plant using a multi-step process.
  • a catalyst composition for use in a process for producing a hydrocarbon product from a feedstock including a lipid, the catalyst composition comprising an Ml-[Sup] catalyst, where Ml is an active metal and [Sup] comprises an acidic support, wherein the acidic support includes a zeolite and/or SAPO, and a refractory inorganic oxide.
  • Ml is selected from one or more of the group comprising platinum, palladium, molybdenum, tungsten, cobalt, nickel, tin and copper.
  • the catalyst composition comprises only one metal Ml on the support.
  • the weight percent of metal Ml present in the acidic support where Ml comprises platinum, palladium, tin or copper is between from about 0.1 to 5 wt.% based on the weight of the catalyst.
  • the weight percent of metal Ml present in the acidic support where Ml comprises cobalt, nickel, molybdenum or tungsten is between from about 2 to 20 wt.% based on the weight of the catalyst.
  • Also provided by a further aspect of the invention is a method of forming a catalyst composition for use in a process for producing a hydrocarbon product from a feedstock including a lipid, the method including the steps of mixing a zeolite and/or SAPO with a refractory inorganic oxide to form an acidic support mixture, and forming the mixture into a support, applying a metal Ml to the support to form the catalyst composition.
  • the step of forming the mixture into a support includes the step of extruding and heating the mixture.
  • the resulting heat-treated mixture is preferably subsequently shaped.
  • the metal Ml is applied to the support using an incipient wetness method.
  • aspects of the invention also provide hydrocarbon product produced by a method described herein.
  • aspects of the invention also provide a catalyst composition produced by a method described herein.
  • apparatus for use in a process for producing a hydrocarbon product from a feedstock including a lipid, the apparatus including a reactor containing a catalyst composition comprising an Ml -[Sup] catalyst, where Ml is an active metal and [Sup] comprises an acidic support, and further including a separator downstream of the reactor.
  • the separator may comprise one or more separator units.
  • the reactor may comprise a reactor system, the reactor system including one or more reactor elements.
  • a further catalyst composition may be contained in the reactor or a reactor element of the system.
  • the further catalyst composition may comprise an M2- [Supi] catalyst, where M2 is an active metal and [Supi] comprises an acidic support.
  • M2 may be different from Ml .
  • [Supi] may be different from [Sup].
  • the reactor system may comprise two or more reactor elements, the two or more reactor elements containing different catalyst compositions.
  • the inventors have identified that reducing strong Lewis acid sites on the acidic support, by modulating the acidity of, for example the molecular sieve, is helpful for preparing a preferred catalyst for use in aspects of the invention, over which
  • hydrodeoxygenation will be inhibited and the selectivity of hydrodecarbonylation plus hydrodecarboxylation reactions will increase.
  • the support material preferable has weak or medium acidity.
  • the support material is a less strong Lewis acid and a more strong Bransted acid.
  • the support material has pores extending substantially in one dimension.
  • the support material may have substantially one-dimensional pores having an axis between from 3.0 to 7.0 A. More generally, preferably the pore diameter is between from 3.0 to 7.0 A.
  • oxygen atoms of a lipid may in examples mainly be removed through hydrodecarbonylation and hydrodecarboxylation, and the generated paraffins will be hydroisomerized substantially simultaneously.
  • a single-step process of directly converting the lipid to iso-paraffins with high cetane value, low freezing point, low aromatics and low sulfur may thus be achievable in some examples.
  • the invention extends to methods, compositions and/or apparatus substantially as herein described preferably with reference to the accompanying figures.
  • Figure 1 shows schematically an example of apparatus for use a process scheme for a single-step process for the production of a biodiesel
  • Figure 2 shows liquid product distribution analysis by GC-MS for the product of Example 2
  • Figure 1 shows schematically an example of apparatus for use in a process scheme for a single-step process for the production of a biodiesel.
  • the apparatus includes three units A, B and C as illustrated in Figure 1. It will be understood that practical examples of apparatus of the type illustrated in Figure 1 may include additional units or other elements.
  • the apparatus includes a fixed-bed reactor A filled with catalyst 100.
  • a feed stream 1 is fed to the reactor A together with a recycled hydrogen-containing stream 2.
  • the feedstream 1 including the feedstock with hydrogen from the hydrogen-containing stream 2 over the catalyst 100 in the reactor A and undergoes hydrogenation, deoxygenation and hydroisomerization substantially simultaneously.
  • a product stream 3 is generated, the product stream including iso-paraffins, normal-paraffins, water, propane, carbon dioxide, and carbon monoxide.
  • the product stream 3 is passed from the base of the reactor A to a liquid product separator B, in which a diesel-range paraffin-containing stream 6, a gasoline-range paraffin-containing stream 7 and a water-containing stream 5 are separated from the product stream 3.
  • a gaseous product stream 4 is fed from the liquid product separator B to a gas separator C.
  • a hydrogen-containing stream 2 is generated and fed to the reactor A, by which method hydrogen is recycled back to the reactor A.
  • Catalyst Preparation SAPO-11 and ZSM-22 zeolite were synthesized according to the directions of Flanigen et al. (Pure Appl. Chem. 58 (1986) 1351-1358) and Kokotailo et al. (Zeolites 5 (1985) 349-351).
  • the synthesized zeolite was blended with 30wt/% ⁇ - ⁇ 1 2 0 3 (produced by Shandong Aluminium Industry Co., Ltd.) and the mixture was extruded and calcined before being used as the support. All of the related catalysts were prepared by incipient wetness impregnation method to prepare the compositions indicated in the examples below.
  • the incipient wetness impregnation method is a known method for impregnating catalyst supports. It comprises for example the steps of adding a solution of catalyst metal Ml for example as a water soluble salt to a support in such a manner that the support remains dry in behaviour.
  • the liquid is taken up into the pores of the support and preferably does not form a significant film on the outside of the catalyst. Subsequent removal of the solvent with, for example vacuum or nitrogen and/or heating leaves the catalyst precursor predominately in the pores.
  • a calcination treatment may be carried out.
  • the calcination treatment may include heating to a temperature of between from 450 to 800 ° C for 2 to 24 h under oxygen or air atmosphere, for example between from 500 to 600 ° C for 4 to 12 h under oxygen or air atmosphere.
  • a lower temperature for example between from 300 to 800 ° C might be used.
  • the following describes a two-step process for producing second generation biodiesel and/or biojet from soybean oil.
  • Refined soybean oil (produced by China Oil & Foodstuffs Corporation (COFCO), third grade, up to National Standard GB1535-2003) with a fatty acid composition of 0.1% lauric, 0.1% myristic, 10.2% palmitic, 3.7% stearic, 22.8% oleic, 53.7% linoleic and 8.6% linolenic and an acid value of 0.2 mgKOH.g "1 (as measured by ASTM D974) was fed to a fixed-bed reactor (10 mm i.d. (internal diameter) and 600 mm in length) with a 5wt.%Ni- 5wt.%Mo/y-A1203 catalyst (7.8 g, 10 mL, 10-20 meshes).
  • COFCO China Oil & Foodstuffs Corporation
  • the reaction was operated at a LHSV (liquid hourly space velocity determined as the volume of liquid feed/h divided by the volume of the catalyst) of 0.5 h "1 , 355 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L.
  • LHSV liquid hourly space velocity determined as the volume of liquid feed/h divided by the volume of the catalyst
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 28.8%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product (determined using GC-MS) was 0.4.
  • the liquid product contained 13.8wt.% of water and 86.2wt.% of organic product wherein the content of iso-paraffins was 1.7wt.% and the content of normal-paraffins was 97.3wt.%.
  • the liquid product was separated, and the purified product consisting of paraffins was obtained.
  • the purified product consisting of paraffins was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a 0.5wt.%Pt/SAPO-l 1 catalyst (8.2 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 1 h "1 , 365 ° C, 4.0 MPa and a H 2 /oil ratio of 1353 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • a single-step process for producing second generation biodiesel and/or biojet from soybean oil over a Pt/SAPO-11 catalyst is described.
  • Refined soybean oil (produced by COFCO, third grade, up to National Standard GB1535-2003) was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a lwt.%Pt/SAPO-l 1 catalyst (7.5 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 1 h "1 , 357 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • the results were as follows: the soybean oil conversion was 100%, the
  • a single-step process for producing second generation biodiesel and/or biojet from soybean oil over a Pt/SAPO-11 catalyst is described.
  • Refined soybean oil (produced by COFCO, third grade, up to National Standard GB1535-2003) was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a 1 wt.%Pt/SAPO-l 1 catalyst (8.1 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 0.6 h "1 , 339 ° C, 6.0 MPa and a H 2 /oil ratio of 1765 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • GB1535-2003 was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a 0.5 wt.% PT/SAPO-11 catalyst (8. lg, 10 mL, 10-20 mesh).
  • the reaction was operated at a LHSV of 0.6 h "1 , 364 °C, 6.0 MPa and a H 2 /oil ration of 1353 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • a single-step process for producing second generation biodiesel and/or biojet from soybean oil over Pd/SAPO-1 1 catalyst is described.
  • Refined soybean oil (produced by COFCO, third grade, up to National Standard GB 1535-2003) was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a lwt.%Pd/SAPO-l 1 catalyst (8.7 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 0.6 h "1 , 350 ° C , 6.0 MPa and a H 2 /oil ratio of 1353 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 52.7%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 1.1.
  • the yield of Cii-C 24 paraffins was 79.6wt.%>, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from coconut oil over a Pt-Pd/SAPO-1 1 catalyst is described.
  • the reaction was operated at a LHSV of 1 h "1 , 357 ° C , 4.0 MPa and a H 2 /oil ratio of 1765 NL/L. After 3 hours, the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 86.5%>, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 6.4.
  • the yield of C11-C24 paraffins was 76.8wt.%, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from rice bran oil over Pt/ZSM-22 catalyst is described.
  • the reaction was operated at a LHSV of 1 h "1 , 357 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L. After 3 hours, the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC -MS.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 71.4%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 2.5.
  • the yield of Cii-C 24 paraffins was 75.7wt.%, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from soybean oil over Pt/SAPO-11 and Pd/SAPO-11 is described.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 78.4%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 3.6.
  • the yield of C11-C24 paraffins was 80.2wt.%, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from soybean oil over Pt-Ni/SAPO-11 catalyst is described.
  • GB1535-2003 was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a lwt.%Pt-5wt.%Ni/SAPO-l l catalyst (7.6 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 0.6 h "1 , 339 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 77.5%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 3.4.
  • the yield of Ci i-C 24 paraffins was 76.3wt.%, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from waste oil over Ni-Mo/SAPO-11 catalyst is described.
  • the reaction was operated at a LHSV of 0.6 h "1 , 355 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L.
  • the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • the results were as follows: the waste oil conversion was 99.8%, the hydrodecarbonylation plus hydrodecarboxylation selectivity was 51.7%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product was 1.1.
  • the yield of C11-C24 paraffins was 79.8wt.%, and the isomers content of Cn-C 24 paraffins was
  • a single-step process for producing second generation biodiesel and/or biojet from animal fat over Ni-Mo/SAPO-11 catalyst is described.
  • the lard and tallow fat mixture (produced by Tianjin Lihongde Lipid Co., Ltd., up to National Standard GV10145-2005) with a fatty acid composition of 21.2% palmitic, 18.5% stearic, 45.5% oleic and 11.2% linoleic and a acidic value of 0.3 mgKOH-g " 1 was fed to a fixed-bed reactor (10 mm i.d. and 600 mm in length) with a 5wt.%Ni-10wt.%Mo/SAPO- 11 catalyst (8.2 g, 10 mL, 10-20 meshes).
  • the reaction was operated at a LHSV of 0.6 h "1 , 365 ° C, 4.0 MPa and a H 2 /oil ratio of 1765 NL/L. After 3 hours, the gas product was collected and analyzed by GC-TCD, while the liquid product was collected and analyzed by GC and GC-MS.
  • hydrodecarbonylation plus hydrodecarboxylation selectivity was 52.6%, and the ratio of odd-numbered paraffins product to even-numbered paraffins product is 1.1.
  • the yield of C11-C24 paraffins was 79.2wt.%, and the isomers content of Cn-C 24 paraffins was
  • Examples of the present invention provide a process for producing hydrocarbon product, for example product for use as, or as a component in, biodiesel and/or biojet.
  • the main components of the hydrocarbon product are iso-paraffins.
  • the hydrocarbon products are produced from a feedstock including a lipid, for example a fatty acid oil.
  • catalytically hydrogenating is a process for producing hydrocarbon product, for example product for use as, or as a component in, biodiesel and/or biojet.
  • the main components of the hydrocarbon product are iso-paraffins.
  • the hydrocarbon products are produced from a feedstock including a lipid, for example a fatty acid oil.
  • deoxygenating and hydroisomerizing the lipid feedstock to paraffins may be carried out in a single step.
  • a character of examples of the process is that the oxygen atoms of the lipid are mainly converted to CO and C0 2 , and less are converted to H 2 0.
  • Examples of the present single-step process can produce biodiesel and/or biojet with a high cetane value, low freezing point, low aromatics and low sulfur. More particularly, the hydrogen consumption of examples of the single-step process is less than that of a conventional two- step hydrogenation process.

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Abstract

La présente invention concerne un procédé de production d'un produit hydrocarboné. Dans des exemples, le procédé comprend la mise en contact d'une charge avec une composition catalytique en présence d'hydrogène, la charge comprenant un lipide, et la composition catalytique étant active pour la conversion du lipide en produit hydrocarboné en une seule étape. La composition catalytique comprend un catalyseur M1-[Sup], M1 étant un métal actif et [Sup] comprenant un support acide. Dans les exemples décrits, le procédé est utilisé dans la production d'un carburant pour un moteur diesel et/ou d'un carburant pour un moteur à réaction à partir d'un lipide ayant un rendement élevé d'alcanes ramifiés en C11-C24 avec un indice de cétane élevé et un bas point de congélation. Dans des exemples, le produit hydrocarboné comprend plus de 70 % en poids d'alcanes en C11-C24 sur la base du poids du lipide, et la teneur en alcanes ramifiés des alcanes en C11-C24 est supérieure à 60 % en poids des alcanes ramifiés en C11-C24 sur la base du poids des alcanes en C11-C24.
PCT/CN2012/071759 2012-02-24 2012-02-29 Conversion de lipides WO2013123678A1 (fr)

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